CN107925037A - Non-aqueous secondary battery adhesive composition, non-aqueous secondary battery functional layer composition, non-aqueous secondary battery functional layer and non-aqueous secondary battery - Google Patents

Non-aqueous secondary battery adhesive composition, non-aqueous secondary battery functional layer composition, non-aqueous secondary battery functional layer and non-aqueous secondary battery Download PDF

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CN107925037A
CN107925037A CN201680046405.6A CN201680046405A CN107925037A CN 107925037 A CN107925037 A CN 107925037A CN 201680046405 A CN201680046405 A CN 201680046405A CN 107925037 A CN107925037 A CN 107925037A
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functional layer
secondary battery
aqueous secondary
water
mass
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CN107925037B (en
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大久保雄辉
高松裕美
丰田裕次郎
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Zeon Corp
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Nippon Zeon Co Ltd
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    • C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
    • C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C08L2201/50—Aqueous dispersion, e.g. containing polymers with a glass transition temperature (Tg) above 20°C
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
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    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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Abstract

It is an object of the invention to provide the non-aqueous secondary battery adhesive composition that can form the functional layer that energy is caught with high transition metal and electrode composite material layer.The non-aqueous secondary battery adhesive composition of the present invention is characterized in that, contain water-soluble polymer and water, what above-mentioned water-soluble polymer included more than 10 mass % and below 50 mass % contains sulfonic monomeric unit, and (methyl) acrylonitrile monomer unit comprising more than 20 mass %.

Description

Non-aqueous secondary battery adhesive composition, non-aqueous secondary battery functional layer are used Composition, non-aqueous secondary battery functional layer and non-aqueous secondary battery
Technical field
The present invention relates to non-aqueous secondary battery adhesive composition, non-aqueous secondary battery functional layer composition, Non-aqueous secondary battery functional layer and non-aqueous secondary battery.
Background technology
The non-aqueous secondary batteries such as lithium rechargeable battery (it is following, sometimes referred to simply as " secondary cell ".) with small-sized, light Matter and energy density height and then rechargeable characteristic, are used in extensive purposes.Moreover, secondary cell usually has Standby electrode (cathode, anode) with electrode composite material layer and positive electrode and negative electrode are isolated and are prevented between positive electrode and negative electrode The battery components such as the distance piece of short circuit.In addition, the battery components with functional layers such as porous membrane layer, adhesive linkages are used in recent years, Above-mentioned porous membrane layer is used to improve heat resistance, intensity, and above-mentioned adhesive linkage is used to improve the cementability between battery components.
Here, in order to make component in above-mentioned battery components, battery components be bonded to each other, use viscous with caking property Tie material.Moreover, in order to realize that the further performance of secondary cell improves, it is try in electrode composite material layer, function The improvement (see, for example patent document 1~2) of binding material used in the formation of layer.
In patent document 1, it is proposed that following technology：Formed by using water-soluble polymer as binding material more Pore membrane layer, so as to suppress the generation of the gas as caused by halide ion in electrolyte etc., above-mentioned water-soluble polymer includes The amide monomer units of the weight % of the monomeric unit containing acidic group of the weight % of 20 weight %~80 and 0.1 weight %~10.
In patent document, it is proposed that following technology：Cathode composite wood is formed by using cathode adhesive composition The bed of material, so as to suppress the generation of condensation product, improves the electrical characteristics of secondary cell, above-mentioned cathode adhesive composition contains viscous Tie material, organic dispersion medium and lithium, above-mentioned binding material includes the acidic-group that has of 10 mass %~35 mass % Ethylenically unsaturated monomer and there is defined weight average molecular weight, above-mentioned lithium is worked as relative to the acidic-group of binding material for regulation Amount.
Prior art literature
Patent document
Patent document 1：International Publication No. 2014/196436；
Patent document 2：International Publication No. 2014/185072.
The content of the invention
The subject that the invention solves
In recent years, from viewpoints such as the high capacities of secondary battery capacity, the electrode as the cathode of secondary cell is answered Condensation material layer (anode composite material layer), using comprising the positive active material containing transition metal (for example, LiCoO2、 LiNiO2, Co-Ni-Mn lithium-contained composite oxide etc.) anode composite material layer.But contain transition metal using In the secondary cell of positive active material, exist due to the transition gold with its side reaction used etc. and in positive active material Belong to (for example, cobalt, nickel, manganese) as the situation in transition metal ions dissolution to electrolyte.Moreover, from cathode dissolution to electrolyte In transition metal be possible to separate out on anode, cause the deterioration of the battery behaviors such as the cycle characteristics of secondary cell.
However, in the prior art, for secondary cell, it is conceived to by improving the physical property of battery components itself to make The problem of technology that the performance of secondary cell improves, dissolution for above-mentioned transition metal, do not study fully.Cause This, in the secondary cell using the positive active material containing transition metal, it is desirable to which offer will be from positive active material dissolution Transition metal ions the transition metal ions to anode move before or reach anode when catch, prevent from separating out in anode Cross the technology of metal.
Solutions to solve the problem
Therefore, the present inventor is caught the transition metal ions in from positive active material dissolution to electrolyte with providing Had made intensive studies for the purpose of technology.Then, inventors have contemplated that electrode composite material layer, structure by making composition electrode There is the capture function of transition metal ions into the functional layer of electrode or distance piece, so that will be from positive active material dissolution to electricity Transition metal ions in solution liquid is caught in the secondary battery.In addition, the present inventor further studies repeatedly, use is had been found that The adhesive composition for making following water-soluble polymer be dissolved in the water and be formed, then can form and play high transition metal The electrode composite material layer and functional layer of energy are caught, so as to complete the present invention, above-mentioned water-soluble polymer is respectively with specific Ratio is included containing sulfonic monomeric unit and (methyl) acrylonitrile monomer unit.
That is, the present invention is advantageously will to solve the above subject as a purpose, and non-aqueous secondary battery of the invention is used viscous Knot agent composition be characterized in that, containing water-soluble polymer and water, above-mentioned water-soluble polymer include more than 10 mass % and Below 50 mass %'s contains sulfonic monomeric unit, and (methyl) acrylonitrile monemer list comprising more than 20 mass % Member.If contain sulfonic monomeric unit and (methyl) acrylonitrile monemer using making to include with specific ratio respectively like this The adhesive composition that the water-soluble polymer of unit is dissolved in the water and is formed, then can be to electrode composite material layer, function Layer assigns high transition metal and catches energy.
In addition, in the present invention, " including monomeric unit " means " in the polymer obtained from using the monomer, to wrap Containing the repetitive unit from monomer ".In addition, in the present invention, " (methyl) acrylonitrile " means acrylonitrile and/or metering system Nitrile.Moreover, in the present invention, polymer refers to being dissolved in the polymer of 0.5g at 25 DEG C the water of 100g for " water solubility " Insoluble component is less than 0.5 mass % when middle.
Here, in the non-aqueous secondary battery adhesive composition of the present invention, preferably above-mentioned water-soluble polymer exists Swellbility in non-aqueous electrolyte is more than 2 times and less than 5 times.If the use of the swellbility in non-aqueous electrolyte is 2 The above and less than 5 times of water-soluble polymer again, then can further improve and be answered using electrode obtained from adhesive composition Condensation material layer, the transition metal of functional layer catch energy, and improve the cementability after electrolyte dipping, make following for secondary cell Ring property improves.
In addition, in the present invention, " swellbility in non-aqueous electrolyte " of water-soluble polymer can be used as will be right The film (adhensive membrane) that water-soluble polymer is molded with is impregnated in defined non-aqueous electrolyte under prescribed conditions Situation dipping after weight divided by the weight before dipping value (again) and obtain, specifically, use the reality of this specification The method molding adhesive film described in example is applied, is measured using the assay method described in same embodiment.
Moreover, the non-aqueous secondary battery of the present invention preferably further contains particle shaped polymer with adhesive composition. If, can be to work(using the above-mentioned adhesive composition that particle shaped polymer is also included in addition to comprising water-soluble polymer Ergosphere and electrode composite material layer assign flexibility, it is ensured that the front and rear cementability of both of electrolyte dipping of these layers.
In addition, the present invention is advantageously will to solve the above subject as a purpose, non-aqueous secondary battery work(of the invention Ergosphere composition is characterized in that, contains above-mentioned any non-aqueous secondary battery adhesive composition and non-conductive Particle.Used using the functional layer containing above-mentioned any non-aqueous secondary battery adhesive composition and non-conductive particles Functional layer obtained from composition plays a role well as the porous membrane layer of heat resistance, excellent strength, and plays high Transition metal catches energy.
Here, the non-aqueous secondary battery functional layer composition of the present invention is preferably with respect to the above-mentioned non-of 100 mass parts Electroconductive particle, containing more than 1 mass parts and 10 above-mentioned water-soluble polymers below mass part.If functional layer composition In non-conductive particles and water-soluble polymer use level ratio in above-mentioned scope, then functional layer can be further improved Transition metal catch can, and make thermal shrinkage and the raising of Ge Erlai values, improve the cycle characteristics and multiplying power of secondary cell Characteristic.
In addition, the present invention is advantageously will to solve the above subject as a purpose, non-aqueous secondary battery of the invention is used Functional layer is characterized in that it is formed using above-mentioned any non-aqueous secondary battery functional layer composition.Make The non-aqueous secondary battery formed with above-mentioned any non-aqueous secondary battery functional layer composition has with functional layer High transition metal catches energy, and the porous membrane layer as heat resistance, excellent strength plays a role well in addition.
In addition, the present invention is advantageously will to solve the above subject as a purpose, non-aqueous secondary battery of the invention It is characterized in that there is above-mentioned non-aqueous secondary battery functional layer.With above-mentioned non-aqueous secondary battery functional layer The battery behaviors such as the cycle characteristics of non-aqueous secondary battery are excellent.
Invention effect
In accordance with the invention it is possible to provide the functional layer and electrode composite material that can be formed and energy is caught with high transition metal The non-aqueous secondary battery adhesive composition of layer.
In addition, in accordance with the invention it is possible to provide the non-water system that can form the functional layer that energy is caught with high transition metal Secondary cell functional layer composition.
Moreover, used in accordance with the invention it is possible to provide the non-aqueous secondary battery with high transition metal seizure energy Layer and with the non-aqueous secondary battery functional layer and the excellent non-aqueous secondary battery of the battery behavior such as cycle characteristics.
Embodiment
Hereinafter, embodiments of the present invention are described in detail.
Here, the non-aqueous secondary battery of the present invention can be used for electrode composite material layer, non-water system with adhesive composition The formation of secondary cell functional layer, above-mentioned electrode composite material layer are formed on the collector of electrode, and above-mentioned non-water system is secondary Battery is formed on the electrode composite material layer (i.e. on electrode base material) or on distance piece base material with functional layer.It is moreover, of the invention Non-aqueous secondary battery functional layer with composition include the present invention non-aqueous secondary battery adhesive composition, can be used as Prepare the material during non-aqueous secondary battery functional layer of the present invention.In addition, the non-aqueous secondary battery function of the present invention Layer is to be prepared using the non-aqueous secondary battery functional layer of the present invention with composition, forms the one of such as distance piece, electrode Part.Moreover, the non-aqueous secondary battery of the present invention has the non-aqueous secondary battery functional layer of the present invention.
(non-aqueous secondary battery adhesive composition)
The non-aqueous secondary battery adhesive composition of the present invention is characterized in that it is that water-soluble polymer is dissolved in The composition formed in water, the water-soluble polymer include more than 10 mass % and below 50 mass % containing sulfonic Monomeric unit, and (methyl) acrylonitrile monomer unit comprising more than 20 mass %.
Moreover, electrode composite material layer, functional layer are formed by using the adhesive composition of the present invention, so as to These layers is played high transition metal and catch energy.In addition, the water-soluble polymer in the adhesive composition of the present invention has Excellent caking property, therefore the adhesive composition of the present invention is as binder composition for electrode and functional layer binding agent group Any of compound can use well.On the other hand, from by cathode dissolution transition metal ions reach anode it It is preceding reliably caught from the viewpoint of, adhesive composition of the invention is preferred for anode composite material layer or functional layer Formation, be more preferably used for the formation of functional layer.That is, adhesive composition of the invention is preferably cathode adhesive composition Or functional layer adhesive composition, it is more preferably functional layer adhesive composition.Hereinafter, for the binding agent group of the present invention Compound, enumerates and is illustrated in case of the adhesive composition is used for the formation of functional layer.
<Water-soluble polymer>
Water-soluble polymer includes the sulfonic monomeric unit that contains of more than 10 mass % and below 50 mass %, and (methyl) acrylonitrile monomer unit comprising more than 20 mass %, can optionally include containing sulfonic monomeric unit and Monomeric unit beyond (methyl) acrylonitrile monomer unit.There is such monomer composition by water-soluble polymer, so that work( The transition metal of ergosphere catches and can improve.In addition, the functional layer comprising the water-soluble polymer with such monomer composition by It is excellent in adhesion before electrolyte dipping, therefore dry linting can be adequately suppressed, the functional layer can be (special to battery components in addition It is not distance piece) assign excellent thermal shrinkage.And then water-soluble polymer is due to being dissolved in water-based binding agent combination In thing, water-based functional layer composition, so its water-insoluble polymer with water-medium being usually in particle shape It is different, it is believed that its strand exists with the state being sufficiently spread out in these compositions.Even if thus it is speculated that due to functional layer group Water-soluble polymer also can fully ensure its specific surface area when filling in the secondary battery, so obtained functional layer can be abundant Ground plays transition metal and catches energy.
[containing sulfonic monomeric unit]
Contain sulfonic monomer containing sulfonic monomeric unit as that can be formed, styrene sulfonic acid, second can be enumerated Olefin sulfonic acid, methyl ethylene sulfonic acid, (methyl) allyl sulphonic acid, (methyl) acrylic acid -2- sulfonic acids, 2- acrylamides Base -2- methyl propane sulfonic acids, 3- allyloxy -2- hydroxy-propanesulfonic acids and their salt (lithium salts, sodium salt etc.).These can individually make With a kind, two or more can also be applied in combination.Moreover, in these, from the viewpoint of the cycle characteristics for improving secondary cell, Optimization styrene sulfonic acid, 2- acrylamide-2-methylpro panesulfonic acids and their salt, more preferably styrene sulfonic acid lithium, styrene Sodium sulfonate, further preferred styrene sulfonic acid lithium.
In addition, in the present invention, " (methyl) pi-allyl " means pi-allyl and/or methacrylic, " (methyl) propylene Acid " means acrylic acid and/or methacrylic acid.
Moreover, contain sulfonic monomeric unit ratio shared in whole monomeric units that water-soluble polymer is included Example is needed for more than 10 mass % and below 50 mass %, is preferably more than 15 mass %, more preferably more than 20 mass %, into One step is preferably more than 30 mass %, furthermore it is preferred that being below 45 mass %, is more preferably below 40 mass %.When containing sulphur When the content ratio of the monomeric unit of acidic group is less than 10 mass %, it can not fully ensure that the transition metal of functional layer catches energy, The cycle characteristics of secondary cell declines.On the other hand, when the content ratio containing sulfonic monomeric unit is more than 50 mass % When, agglomerate non-conductive particles with composition in functional layer, the cementability before the electrolyte dipping of functional layer declines.
[(methyl) acrylonitrile monomer unit]
As (methyl) acrylonitrile monemer that can form (methyl) acrylonitrile monomer unit, acrylonitrile and methyl-prop can be enumerated Alkene nitrile.These can be used singly or in combination of two or more.Moreover, in these, from the mistake for improving functional layer Cross metal catch can and make from the viewpoint of the cycle characteristics of secondary cell improves, preferred acrylonitrile.
Moreover, the ratio that (methyl) acrylonitrile monomer unit is shared in whole monomeric units that water-soluble polymer is included Example is needed for more than 20 mass %, is preferably more than 25 mass %, more preferably more than 30 mass %, furthermore it is preferred that being 50 matter Measure below %, more preferably below 40 mass %, more preferably below 35 mass %.When (methyl) acrylonitrile monomer unit Content ratio when being less than 20 mass %, can not fully ensure functional layer transition metal catch can, the circulation of secondary cell Characteristic declines.In addition, the thermal shrinkage of the battery components (particularly distance piece) with functional layer is damaged, particularly in function Layer is used as producing unfavorable condition during porous membrane layer.On the other hand, if the content ratio of (methyl) acrylonitrile monomer unit is Below 50 mass %, the then cementability being able to ensure that before the electrolyte dipping of functional layer.
[other monomeric units]
As containing the monomeric unit beyond sulfonic monomeric unit and (methyl) acrylonitrile monomer unit, do not have special Limit, such as (methyl) acrylate monomeric units can be enumerated, the monomeric unit containing acidic group (removes and contains sulfonic monomer list Beyond member).In addition, other monomeric units can be used singly or in combination of two or more.
[[(methyl) acrylate monomeric units]]
As (methyl) acrylate monomer that can form (methyl) acrylate monomeric units, can enumerate：Acrylic acid first Ester, ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, i-butyl Ester, acrylic acid n-pentyl ester, isoamyl acrylate, Hexyl 2-propenoate, heptylacrylate, 2-ethyl hexyl acrylate, acrylic acid-2-ethyl oneself Ester, acrylic acid nonyl ester, decyl acrylate, dodecylacrylate, n-myristyl base ester, octadecyl acrylate Deng alkyl acrylate；Methyl methacrylate, ethyl methacrylate, n propyl methacrylate, methacrylic acid isopropyl Ester, n-BMA, Tert-butyl Methacrylate, Isobutyl methacrylate, n-amylmethacrylate, methyl-prop Olefin(e) acid isopentyl ester, hexyl methacrylate, metering system heptyl heptylate, 2-Propenoic acid, 2-methyl-, octyl ester, methacrylic acid -2- ethyl hexyls Ester, nonyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate, methacrylic acid n-tetradecane base ester, Alkyl methacrylates such as octadecyl methacrylate, glycidyl methacrylate etc..In these, from raising Cementability before the electrolyte dipping of functional layer, and from the viewpoint of the water solubility of the polymer ensured, be preferably bonded (methyl) alkyl acrylate monomer for being more than 1 and less than 10 in the carbon number of the alkyl of non-carbonyl oxygen atom, it is more excellent Select (methyl) alkyl acrylate monomer that same carbon number is more than 1 and less than 7.Specifically, preferred acrylic acid fourth Ester (n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate), ethyl acrylate, acrylic acid-2-ethyl caproite, it is more excellent Select butyl acrylate, ethyl acrylate, further preferred butyl acrylate.
Moreover, (methyl) acrylate monomeric units are shared in whole monomeric units that water-soluble polymer is included Ratio is preferably more than 15 mass %, and more preferably more than 20 mass %, are more preferably more than 25 mass %, particularly preferably For more than 30 mass %.If the content ratio of (methyl) acrylate monomeric units is more than 15 mass %, can improve Cementability before the electrolyte dipping of functional layer.In addition, the content ratio of (methyl) acrylate monomeric units is needed for 70 matter Below % is measured, is preferably below 65 mass %.
[[monomeric unit containing acidic group]]
As the monomer containing acidic group of the monomeric unit containing acidic group can be formed, as long as contain the acid beyond sulfonic group The monomer of base is just not particularly limited, and can enumerate the monomer with carboxylic acid group, the monomer with phosphate and the list with hydroxyl Body.
As the monomer with carboxylic acid group, can enumerate such as monocarboxylic acid, dicarboxylic acids and their salt (sodium salt, lithium salts). As monocarboxylic acid, such as acrylic acid, methacrylic acid, crotonic acid can be enumerated.As dicarboxylic acids, such as maleic acid, richness can be enumerated Horse acid, itaconic acid.
As the monomer with phosphate, can enumerate such as phosphoric acid -2- (methyl) acryloyloxyethyl ester, phosphoric acid methyl - 2- (methyl) acryloyloxyethyl ester, ethyl-(methyl) acryloyloxyethyl ester and their salt (sodium salt, lithium salts etc.). In addition, in the present invention, " (methyl) acryloyl group " means acryloyl group and/or methylacryloyl.
As the monomer with hydroxyl, such as 2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, methyl can be enumerated 2-Hydroxy ethyl acrylate, methacrylic acid -2- hydroxy propyl esters and their salt (sodium salt, lithium salts etc.).
In these, as the monomer containing acidic group, the preferably monomer with carboxylic acid group, more preferably acrylic acid, methyl-prop Olefin(e) acid, further preferred methacrylic acid.
Moreover, the ratio that the monomeric unit containing acidic group is shared in whole monomeric units that water-soluble polymer is included Preferably more than 0.5 mass %, more preferably more than 1 mass %, more preferably more than 2 mass %, furthermore it is preferred that being 15 Below quality %, more preferably below 10 mass %, more preferably below 8 mass %.If the monomer list containing acidic group The content ratio of member is more than 0.5 mass %, then the caking property of water-soluble polymer improves, and can soak the electrolyte of functional layer The front and rear cementability of both of stain improves.On the other hand, if the content ratio of the monomeric unit containing acidic group is 15 mass % Hereinafter, then the amount of moisture penetrated into secondary cell can be reduced, suppresses the decline of cycle characteristics.
[preparation method of water-soluble polymer]
Water-soluble polymer can be by gathering the monomer composition comprising above-mentioned monomer in the water solvent such as water Close and manufacture.At this time, the content ratio of each monomer in monomer composition can be based on respectively repeating list in water-soluble polymer The content ratio of first (monomeric unit) determines.
Moreover, polymerization methods are not particularly limited, solution polymerization process, suspension polymerization, mass polymerization, breast can be used Any of liquid polymerization etc. method.In addition, as polymerisation, ionic polymerization, radical polymerization, activity can be used certainly By any of base polymerization etc. reaction.
In addition, emulsifying agent, dispersant, polymerization initiator, the additive such as reagent and additive in polymerization used in polymerization can be used it is logical The additive often used.The usage amount of these additives can also be set to usually used amount.Polymerizing condition can be according to polymerization With the appropriate adjusting such as the species of polymerization initiator.
[character of water-soluble polymer]
Swellbility of the water-soluble polymer in non-aqueous electrolyte is preferably more than 2 times, more preferably more than 2.2 times, More preferably more than 2.5 times, furthermore it is preferred that for less than 5 times, more preferably less than 4 times, more preferably less than 3 times. If swellbility of the water-soluble polymer in non-aqueous electrolyte is more than 2 times, water-soluble polymer is electrolysed with non-water system Liquid is compatible well, the specific surface area being also able to maintain that in non-aqueous electrolyte in water-based functional layer composition. Therefore, the transition metal of functional layer catches and can further improve, and can further improve the cycle characteristics of secondary cell.It is another Aspect, if swellbility of the water-soluble polymer in non-aqueous electrolyte is less than 5 times, can ensure that water-soluble polymer Intensity, it is possible to increase the cementability after the electrolyte dipping of functional layer.
In addition, the glass transition temperature of water-soluble polymer is preferably more than -20 DEG C, more preferably more than -10 DEG C, this Outside, it is preferably less than 80 DEG C, more preferably less than 60 DEG C.If the glass transition temperature of water-soluble polymer is above-mentioned model In enclosing, then the cementability before the electrolyte dipping of functional layer can be improved.
In addition, " glass transition temperature " of water-soluble polymer can use the side described in the embodiment of this specification Method is measured.
<The preparation method of non-aqueous secondary battery adhesive composition>
The preparation method of adhesive composition of the present invention is not particularly limited, for example, by the system of water-soluble polymer , can be by water-soluble polymeric in the case of implementing in water-medium, obtaining water-soluble polymer in a manner of aqueous solution The aqueous solution of thing, can also be in the aqueous solution of water-soluble polymer directly as non-aqueous secondary battery adhesive composition Other components are added as needed and are used as non-aqueous secondary battery adhesive composition.In addition, adhesive composition can be with Include the solvent beyond water.In addition, the preparation of the adhesive composition comprising other components can be with functional layer group described later The preparation of compound is carried out at the same time.
Here, as other components, as long as it will not exceedingly influence to have used the battery of the secondary cell of functional layer anti- The component answered just is not particularly limited.In addition, it can also be two or more that the species of above-mentioned other components, which can be a kind,.
As above-mentioned other components, such as particle shaped polymer can be enumerated and (be also referred to as " particle shape binding material ".), wetting Agent, levelling agent, electrolyte decomposition inhibitor etc..
Here, adhesive composition preferably comprises particle shaped polymer.By the way that water-soluble polymer and particle shape are polymerize Thing is used together as binding material, so as to assign flexibility to functional layer, furthermore it is possible to ensure the electrolyte of functional layer The front and rear cementability of both of dipping.Here, particle shaped polymer is usually water-insoluble polymer, in water-medium with Particle shape exists.In addition, in the present invention, polymer refers to dissolving in 25 DEG C of polymer by 0.5g for " water-insoluble " Insoluble component is more than 90 mass % when in the water of 100g.
It is not particularly limited as particle shaped polymer, styrene-butadiene copolymer, acrylonitrile-butadiene can be enumerated The fluoropolymers such as the diene polymers such as copolymer, Kynoar, acrylic acid series polymeric compounds etc..These polymer can be single 1 kind is solely used, can also be mixed with two or more.
Here, the use level ratio of the water-soluble polymer and particle shaped polymer in adhesive composition does not limit especially It is fixed.In adhesive composition, such as the water-soluble polymer relative to 100 mass parts, containing preferably more than 10 mass parts, more It is preferred that the particle shaped polymer more than 20 mass parts, more than further preferred 30 mass parts, in addition containing preferably 100 mass parts with Under, more preferably 70 below mass part, further preferred 50 particle shaped polymers below mass part.If adhesive composition with Use level ratio in above-mentioned scope includes water-soluble polymer and particle shaped polymer, then can fully ensure functional layer Transition metal catches energy, and can improve the flexibility and the front and rear cementability of both of electrolyte dipping of the functional layer.Cause This, can further improve the cycle characteristics of secondary cell.
(non-aqueous secondary battery functional layer composition)
The functional layer of the present invention is following paste compound with composition, which includes at least above-mentioned water Soluble polymer and non-conductive particles, as needed containing optional compositions such as particle shaped polymers, are situated between using water as scattered Matter.
Moreover, the functional layer of the present invention is prepared with adhesive composition of the composition due to the use of the present invention, and wrap Containing above-mentioned water-soluble polymer, so if using the functional layer composition of the present invention, then can be formed with high mistake Cross the functional layer that metal catches energy.In addition, the functional layer composition of the present invention is due to comprising non-conductive particles, using Functional layer functional layer by the use of obtained from composition of the present invention can be sent out well as the porous membrane layer of heat resistance, excellent strength The effect of waving.
<Non-conductive particles>
Here, non-conductive particles be not dissolved in water and secondary cell it is non-aqueous electrolyte, even at these Among can also maintain the particle of its shape.Moreover, non-conductive particles are in terms of electrochemistry due to also stablizing, in secondary electricity It is stable in the presence of under the use environment in pond in functional layer.
Moreover, as non-conductive particles, for example various inorganic particles, organic fine particles can be used.
Specifically, as non-conductive particles, can use beyond inorganic particles and particle shaped polymer described later Both organic fine particles (that is, organic fine particles do not have caking property), but usually using inorganic particles.Wherein, as non-conductive The material of particle, the material for stably existing preferably under the use environment of non-aqueous secondary battery, stablizing in terms of electrochemistry. From such a viewpoint, if enumerating the preferable example of material of non-conductive particles, can enumerate：Aluminium oxide (alumina), aluminium hydrous oxide (boehmite), silica, magnesia (magnesia), calcium oxide, titanium oxide (tit ania)、BaTiO3, ZrO, the oxide particle such as alumina silica composite oxides；The nitride such as aluminium nitride, boron nitride Particle；The covalent keyness crystal particles such as silicon, diamond；The slightly solubility ionic crystals particle such as barium sulfate, calcirm-fluoride, barium fluoride；It is sliding Small bits of clay such as mountain flour, montmorillonite etc..Furthermore, it is possible to element substitution, surface treatment, solid solution are implemented to these particles as needed Body etc..
Above-mentioned non-conductive particles can be used singly or in combination of two or more.Moreover, led as non- Conductive particles, preferably aluminium oxide (alumina) particle.In addition, the particle diameter of non-conductive particles is not particularly limited, can be set to With the prior art used in the identical particle diameter of non-conductive particles.
Functional layer is not particularly limited with the non-conductive particles in composition and the use level of water-soluble polymer ratio. In functional layer composition, such as the non-conductive particles relative to 100 mass parts, containing preferably more than 1 mass parts, more preferably Water-soluble polymer more than 1.5 mass parts, more than further preferred 2 mass parts, in addition containing preferably 10 below mass part, more It is preferred that 8 is below mass part, further preferred 6 water-soluble polymers below mass part.If functional layer composition relative to The non-conductive particles of 100 mass parts contain water-soluble polymers more than 1 mass parts, then the transition metal of functional layer catches energy Further improve, the cycle characteristics of secondary cell further improves.In addition, the battery components with functional layer (are particularly spaced Part) thermal shrinkage improve.On the other hand, if functional layer composition relative to 100 mass parts non-conductive particles Ge Erlai values raising containing 10 water-soluble polymers below mass part, then functional layer, the multiplying power property of secondary cell improve.
<Optional compositions>
Functional layer can also be included optionally with composition in addition to above-mentioned water-soluble polymer and non-conductive particles Component.As above-mentioned optional compositions, as long as it will not exceedingly influence to have used the cell reaction of the secondary cell of functional layer Component be just not particularly limited.In addition, it can also be two or more that the species of above-mentioned optional compositions, which can be a kind,.
As above-mentioned optional compositions, can enumerate " non-aqueous secondary battery functional layer adhesive composition " this Middle component described in as " other components ".That is, the optional compositions such as particle shaped polymer (other components) can be used in viscous The preparation of agent composition is tied, can also be combined when preparing functional layer composition after preparing adhesive composition with binding agent Thing is mixed.
Moreover, in the case where functional layer includes particle shaped polymer as above-mentioned optional compositions by the use of composition, function Layer is not particularly limited with the non-conductive particles in composition and the use level ratio of particle shaped polymer.Combined in functional layer In thing, such as the non-conductive particles relative to 100 mass parts, containing the particle shaped polymer preferably more than 1 mass parts, in addition Contain preferably 6 below mass part, more preferably 5 below mass part, further preferred 4 particle shaped polymers below mass part.Such as Fruit functional layer composition contains particle shaped polymers more than 1 mass parts relative to the non-conductive particles of 100 mass parts, then The flexibility and the front and rear cementability of both of electrolyte dipping of functional layer can be improved.On the other hand, if functional layer group Compound contains the Ge Er of 6 particle shaped polymers, then functional layer below mass part relative to the non-conductive particles of 100 mass parts Lay value improves, and the multiplying power property of secondary cell improves.
<The preparation method of non-aqueous secondary battery functional layer composition>
Functional layer is not particularly limited with the preparation method of composition, usually combines non-aqueous secondary battery with binding agent Thing, non-conductive particles, be added as needed on mixed as the water of decentralized medium, optional compositions and prepare functional layer group Compound.Mixed method is not particularly limited, in order to make each component efficiently disperse, usually using dispersion machine as mixing arrangement Mixed.
Dispersion machine is preferably able to the device that mentioned component is uniformly dispersed and is mixed.If enumerating example, ball can be enumerated Grinding machine, sand mill, pigment dispersion machine, mixing and kneading machine, ultrasonic dispersing machine, homogenizer, planetary stirring machine etc..In addition, from can Add from the viewpoint of high dispersing shear power, can also enumerate the high dispersal device such as ball mill, roller mill, Filmix.
(non-aqueous secondary battery functional layer)
The functional layer of the present invention is formed by above-mentioned non-aqueous secondary battery functional layer composition, such as can be led to Cross by surface of the above-mentioned functional layer composition coated in appropriate base material and after forming film, the film of formation is done It is dry to be formed.That is, functional layer of the invention is formed by above-mentioned functional layer with the dried object of composition, usually contains above-mentioned non-lead Conductive particles, above-mentioned water-soluble polymer, optionally contain above-mentioned other components (optional compositions) such as particle shaped polymer. This, in the case where above-mentioned water-soluble polymer and/or particle shaped polymer contain the monomeric unit of bridging property, should contain friendship The polymer of the monomeric unit of connection property can be in the drying of non-aqueous secondary battery functional layer composition or dry successor It is crosslinked that (that is, non-aqueous secondary battery functional layer can include above-mentioned water-soluble polymeric during the heat treatment that selection of land is implemented The cross-linking agent of thing and/or particle shaped polymer).
In addition, the presence of each component (except the decentralized medium such as water) that is included of the functional layer of the present invention than usually with it is above-mentioned Functional layer composition included in each component presence than identical, each component in functional layer it is preferable exist than Preferable with each component in above-mentioned functional layer composition exists than identical.
Moreover, the functional layer of the present invention has high due to being formed by the functional layer composition of the present invention Transition metal catches energy, and the porous membrane layer as heat resistance, excellent strength plays a role well in addition.In addition, the present invention Functional layer can improve the battery behaviors such as the cycle characteristics of secondary cell.
<Base material>
It is not particularly limited as the base material for forming functional layer, such as use functional layer to be used as composition one of distance piece Point component in the case of, can use distance piece base material as base material, in addition, use functional layer as composition electrode one In the case of partial component, the electrode base material that formation electrode composite material layer forms on a current collector can be used as base Material.In addition, the usage for the functional layer being formed on base material is not particularly limited, for example, can on distance piece base material etc. shape The battery components such as distance piece are directly used as into functional layer, functional layer can also be formed on electrode base material and be used as electrode, also The functional layer that can be will be formed on demoulding base material is peeled off from base material and is attached to other base materials and is used as battery components.
But the viewpoint peeled off the process of demoulding base material from functional layer from omission and improve the manufacture efficiency of battery components goes out Hair, preferably using distance piece base material or electrode base material as base material.
[distance piece base material]
It is not particularly limited as distance piece base material, distance piece base material known to organic spacer part base material etc. can be enumerated.Have Machine distance piece base material is the porous member that is formed by organic material, if the example for enumerating organic spacer part base material, can be enumerated Micro-porous film comprising the vistanexes such as polyethylene, polypropylene, aromatic polyamide resin etc. etc., from the viewpoint of excellent strength Set out, preferably the micro-porous film of polyethylene.In addition, the thickness of organic spacer part base material can be set to arbitrary thickness, usually It is preferably more than 5 μm for more than 0.5 μm, is usually less than 40 μm, is preferably less than 30 μm, more preferably less than 20 μm.
[electrode base material]
It is not particularly limited as electrode base material (positive-pole base material and base material of cathode), can enumerates and form electrode on a current collector The electrode base material that composite layer forms.
Here, the electrode active material (positive active material, negative electrode active material) in collector, electrode composite material layer With electrode composite material layer binding material (anode composite material layer binding material, anode material layer bonding material Material) and on a current collector formed electrode composite material layer method can use known collector, electrode active material, Binding material and method, can enumerate collector for example described in Japanese Unexamined Patent Publication 2013-145763 publications, electrode activity thing Matter, binding material and method.In addition, as electrode composite material layer binding material, binding agent of the invention can be used The water-soluble polymer that composition is included.
[demoulding base material]
It is not particularly limited as the demoulding base material for forming functional layer, known demoulding base material can be used.
<The forming method of non-aqueous secondary battery functional layer>
As the method that functional layer is formed on the base materials such as above-mentioned distance piece base material, electrode base material, can enumerate with lower section Method.
1) by functional layer with surface of the composition coated in distance piece base material or electrode base material, the side being then dried Method；
2) after distance piece base material or electrode base material being impregnated in functional layer composition, method that it is dried；
3) functional layer composition is coated on demoulding base material, it is dried and manufactures functional layer, by what is obtained The method that functional layer is transferred to the surface of distance piece base material or electrode base material；
In these, from the viewpoint of the thickness of functional layer is easy to control, particularly preferred above-mentioned method 1).In detail and Speech, the method 1) have functional layer with composition coated in process (the coating work on distance piece base material or electrode base material Sequence), make dry coated in the functional layer composition on distance piece base material or electrode base material and form the process (function of functional layer Layer formation process).
[working procedure of coating]
In working procedure of coating, functional layer is not particularly limited with composition coated in the method on base material, example can be enumerated Such as doctor blade method, reverse the methods of roll coating process, direct roll coating process, gravure method, extrusion, spread coating.
[functional layer formation process]
In addition, in functional layer formation process, as the method that the functional layer on base material is dried with composition, do not have It is particularly limited to, known method can be used, can be enumerated：Utilize such as warm air, hot wind, low wet wind and the drying carried out；Very Sky is dry；The seasoning carried out using the irradiation of infrared ray, electron beam etc..Drying condition is not particularly limited, drying temperature Preferably 50~100 DEG C, drying time is preferably 5~30 minutes.
In addition, the thickness for the functional layer being formed on base material can be adjusted suitably.
(non-aqueous secondary battery)
The non-aqueous secondary battery of the present invention has above-mentioned non-aqueous secondary battery functional layer of the invention.More specifically For, non-aqueous secondary battery of the invention has cathode, anode, distance piece and electrolyte, above-mentioned non-aqueous secondary battery At least one of the cathode as battery components, anode and distance piece is contained in by the use of functional layer.
The non-aqueous secondary battery of the present invention is due to the non-aqueous secondary battery functional layer with the present invention, circulation The battery behaviors such as characteristic are excellent.
<Cathode, anode and distance piece>
Cathode, anode and at least one of distance piece used in the secondary cell of the present invention have functional layer.It is specific and Speech, as cathode and anode with functional layer, can use the electrode for being arranged at functional layer and being formed on electrode base material, above-mentioned Electrode base material forms electrode composite material layer and forms on a current collector.In addition, as the distance piece with functional layer, can The distance piece formed using functional layer is arranged on distance piece base material.In addition, as electrode base material and distance piece base material, can Use the identical base material of the base material with being enumerated in the item of [base material].
In addition, as cathode, anode and distance piece without functional layer, it is not particularly limited, can uses by above-mentioned The electrode that is formed of electrode base material and the distance piece that is formed by above-mentioned distance piece base material.
<Electrolyte>
As electrolyte, usually can be used organic electrolyte supporting electrolyte being dissolved in organic solvent.As branch Electrolyte is held, lithium salts can be used in such as lithium rechargeable battery.As lithium salts, such as LiPF can be enumerated6、LiAsF6、 LiBF4、LiSbF6、LiAlCl4、LiClO4、CF3SO3Li、C4F9SO3Li、CF3COOLi、(CF3CO)2NLi、(CF3SO2)2NLi、 (C2F5SO2) NLi etc..Wherein, LiPF6、LiClO4、CF3SO3Li shows high dissociation degree due to being easily dissolved in solvent, It is preferred that.In addition, electrolyte can be used singly or in combination of two or more.In general, have more high using degree of dissociation Supporting electrolyte, the more elevated tendency of lithium ion conductivity, therefore lithium ion can be adjusted by the species of supporting electrolyte Conductivity.
As the organic solvent used in the electrolytic solution, just it is not particularly limited as long as supporting electrolyte can be dissolved, Such as in lithium rechargeable battery, preferably use：Dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), the carbonates such as propene carbonate (PC), butylene (BC), methyl ethyl carbonate (EMC)；Gamma-butyrolacton, formic acid The esters such as methyl esters；The ethers such as 1,2- dimethoxy-ethanes, tetrahydrofuran；Sulfur-containing compound class such as sulfolane, dimethyl sulfoxide (DMSO) etc.. In addition it is possible to use the mixed liquor of these solvents.Wherein, due to the voltage belt field width that dielectric constant is high, stablizes, it is advantageous to carbon Esters of gallic acid.In general, there is the more elevated tendency of the lower lithium ion conductivity of viscosity of the solvent used, therefore solvent can be passed through Species adjusts lithium ion conductivity.
In addition, it can suitably adjust the concentration of the electrolyte in electrolyte.In addition, it can add in the electrolytic solution known Additive.
<The manufacture method of non-aqueous secondary battery>
Non-aqueous secondary battery can be manufactured for example, by the following manner, i.e. cathode and anode is overlapping across distance piece, root According to needing to be wound it, folding etc. and be put into battery case, inject the electrolyte into battery case, sealed. In addition, the component that at least one component in cathode, anode and distance piece is set to have functional layer.Here, can be according to need The anti-overcurrent element such as porous metal mesh, fuse, PTC element, guide plate etc. are put into battery case and is prevented in battery The pressure in portion rises, crosses discharge and recharge.The shape of battery can be such as Coin shape, coin shape, piece type, cylinder type, square, flat Any of type etc..
Embodiment
Hereinafter, based on embodiment, the present invention is specifically described, but the present invention is not limited to these embodiments.In addition, In the following description, unless otherwise specified, " % " and " part " of expression amount is quality criteria.
In addition, in the polymer for manufacturing the monomer copolymerization of multiple species, repetition that certain monomer polymerization is formed Ratio of the unit (monomeric unit) in above-mentioned polymer unless otherwise specified, usually accounts for the polymer with certain monomer The ratio (addition ratio) of the whole monomers used in polymerization is consistent.
In embodiment and comparative example, swellbility and glass transition temperature of the water-soluble polymer in non-aqueous electrolyte Degree, functional layer electrolyte dipping before and electrolyte dipping after cementability, the transition metal of functional layer catch can, distance piece The cycle characteristics of thermal shrinkage and lithium rechargeable battery is measured and is evaluated with following methods.
<Swellbility in non-aqueous electrolyte>
In the water for the water-soluble polymer that thermostatic constant wet chamber's (25 DEG C, humidity 50%) makes to be added in the aluminum dish of diameter 5cm Solution is dried 2 days, obtains the film of thickness 1mm.The film is cut out as 1.5cm × 1.5cm, adhensive membrane, measure weight M0 is made. Then, 60 DEG C by obtained adhensive membrane in non-aqueous electrolyte (solvent：EC/DEC/ vinylene carbonates (VC)=68.5/ 30/1.5 (volume ratio), electrolyte：The LiPF of concentration 1M6) in dipping 72 it is small when.By the non-of the surface of the adhensive membrane after dipping Aqueous electrolyte is wiped, measure weight M1.Then, the swellbility in non-aqueous electrolyte is calculated according to following formula.
Swellbility=M1/M0 in non-aqueous electrolyte
<Glass transition temperature>
In the environment of 50% humidity, 23~25 DEG C, the aqueous solution of water-soluble polymer is dried 3 days, obtain thickness 1mm Film.When making film drying 1 small using 120 DEG C of hot-air oven.Will by dry film as sample, based on JIS K7121, Under conditions of -100 DEG C~180 DEG C of measuring temperature, 5 DEG C/min of programming rate, Differential Scanning Calorimetry analyzer is used (DSC6220SII, the manufacture of Nanotechnolo gy companies) measure glass transition temperature (DEG C).
<Cementability before electrolyte dipping>
Distance piece (having functional layer on distance piece base material) is cut out as the rectangle of wide 10mm × long 100mm, is made Test film.The test film is attached into adhesive tape in a manner of the surface of functional layer is directed downwardly on the surface of functional layer.At this time, use The adhesive tape of JIS Z1522 defineds is as adhesive tape.In addition, adhesive tape is fixed on horizontal testing stand.Then, survey Stress when determining to stretch one end of distance piece along 180 ° of directions with the draw speed of 10mm/ minutes and peeled off.Carry out Measure 3 times, obtains its average value, as peel strength P1, is evaluated with following benchmark.Peel strength P1 is bigger, Represent that the cementability before electrolyte dipping between functional layer and distance piece base material is more excellent.
A：Peel strength P1 is more than 180N/m
B：Peel strength P1 is 140N/m less than 180N/m
C：Peel strength P1 is 100N/m less than 140N/m
D：Peel strength P1 is less than 100N/m
<Cementability after electrolyte dipping>
Distance piece (having functional layer on distance piece base material) is cut out as the rectangle of wide 10mm × long 100mm, is made Test film.By the test film in electrolyte (solvent：EC/DEC/VC (volumetric mixture ratio)=68.5/30/1.5, electrolyte：Concentration The LiPF of 1M6) in dipping 180 minutes.Then, test film is taken out from electrolyte, will be attached to the electrolyte on the surface of functional layer Wipe.Then, in a manner of the surface of functional layer is directed downwardly adhesive tape is attached on the surface of functional layer.At this time, using JIS The adhesive tape of Z1522 defineds is as adhesive tape.In addition, adhesive tape is fixed on horizontal testing stand.Then, measure will Stress when one end of distance piece is stretched with the draw speed of 50mm/ minutes and peeled off along vertical direction.It is measured 3 It is secondary, its average value is obtained, as peel strength P2, is evaluated with following benchmark.Peel strength P2 is bigger, represents Cementability after electrolyte dipping between functional layer and distance piece base material is more excellent.
A：Peel strength P2 is more than 9.0N/m
B：Peel strength P2 is 8.0N/m less than 9.0N/m
C：Peel strength P2 is 6.0N/m less than 8.0N/m
D：Peel strength P2 is less than 6.0N/m
<Transition metal catches energy>
Distance piece (having functional layer on distance piece base material) is cut out as area 100cm2Size, test piece, Measure the weight of the test film.Then, the LiPF as supporting electrolyte is made6Solvent is dissolved in the concentration of 1 mol/L In electrolyte obtained from (EMC: EC=70: 30 (mass ratio)), make cobalt chloride (anhydrous) (CoCl2), nickel chloride (anhydrous) (NiCl2) and manganese chloride (anhydrous) (MnCl2) dissolved in a manner of each concentration of metal ions respectively becomes 20 mass ppm, prepare Measure electrolyte.Then, the above-mentioned measure of 10g is added in the glass container equipped with test film with electrolyte, makes examination Test piece to be impregnated in measure electrolyte, 5 days are stood at 25 DEG C.Then, test film is taken out, test film is fully cleaned with DEC, will Be attached to test film surface DEC fully wipe after, measure the weight of the test film.Then, test film is put into Teflon (note Volume trade mark) in property beaker, sulfuric acid and nitric acid (sulfuric acid: nitric acid=0.1: 2 (volume ratios)) are added, is heated with hot plate, concentrate It is carbonized to test film.After further adding nitric acid and perchloric acid (nitric acid: perchloric acid=2: 0.2 (volume ratio)), perchloric acid is added With hydrofluoric acid (perchloric acid: hydrofluoric acid=2: 0.2 (volume ratio)), generation white cigarette is concentrated into.Then, nitric acid and ultra-pure water are added (nitric acid: ultra-pure water=0.5: 10 (volume ratios)), is heated.After letting cool, constant volume is carried out, constant volume solution is made.It is fixed using this Hold solution, using in the above-mentioned constant volume solution of ICP mass-synchrometers (Pe rkinElmer company systems " ELAN DRS II ") measure Cobalt amount, nickel amount and manganese amount.Then, by by total divided by above-mentioned experiment of the cobalt amount in above-mentioned constant volume solution, nickel amount and manganese amount The weight of piece, so as to calculate the transiting metal concentration (quality ppm) in test film, is evaluated with following benchmark.The transition Metal concentration is higher, represents that the transition metal seizure of the per unit mass of functional layer can be higher.
A：Transiting metal concentration is more than 2500 mass ppm
B：Transiting metal concentration is 1500 mass ppm less than 2500 mass ppm
C：Transiting metal concentration is 500 mass ppm less than 1500 mass ppm
D：Transiting metal concentration is less than 500 mass ppm
<Thermal shrinkage>
Distance piece (having functional layer on distance piece base material) is cut out to the square for being 12cm for the length of side, it is such just Describe the square that the length of side is 10cm, test piece in square inside.Then, test film is put into 150 DEG C of thermostat Place 1 it is small when after, by be depicted in inside square area change (={ (after square area-placement before placement Square area)/place before square area × 100%) obtained as percent thermal shrinkage, carried out with following benchmark Evaluation.The percent thermal shrinkage is smaller, represents that the thermal shrinkage of the distance piece with functional layer is more excellent.
A：Percent thermal shrinkage is less than 5%
B：Percent thermal shrinkage is for 5% less than 10%
C：Percent thermal shrinkage is for 10% less than 20%
D：Percent thermal shrinkage is more than 20%
<Cycle characteristics>
Make the lithium rechargeable battery of manufacture stood in the environment of 25 DEG C 24 it is small when after, in the environment of 25 DEG C, carry out 4.4V is charged to the rate of charge of 0.1C, be discharged to the discharge-rate of 0.1C 2.75V discharge and recharge operation, measure is initial Capacity C 0.Then, further in the environment of 60 DEG C, the operation of same discharge and recharge is repeated, after measuring 1000 circulations Capacity C 1.
Then, the front and rear capacity maintenance rate Δ C (=(C1/C0) × 100%) of circulation is calculated, is commented with following benchmark Valency.The value of capacity maintenance rate Δ C is bigger, represents that the high-temperature cycle of secondary cell is more excellent, the service life is longer.
A：Capacity maintenance rate Δ C is more than 85%
B：Capacity maintenance rate Δ C is for 80% less than 85%
C：Capacity maintenance rate Δ C is for 75% less than 80%
D：Capacity maintenance rate Δ C is less than 75%
(embodiment 1)
<The preparation of non-aqueous secondary battery adhesive composition>
In the 5MPa pressure vessels with mixer, add 30 parts as the styrene sulphur for containing sulfonic monomer Sour lithium, 35 parts of the acrylonitrile as (methyl) acrylonitrile monemer, 30 parts of the acrylic acid as (methyl) acrylate monomer Butyl ester, 5 parts of the methacrylic acid as the monomer for containing acidic group, 1.0 parts of the polyoxygenated as reactive surfactant Alkene alkenyl ether ammonium sulfate, 400 parts of ion exchange water and 1.0 parts of the potassium peroxydisulfate as polymerization initiator, are sufficiently stirred Afterwards, 65 DEG C are heated to, triggers polymerization.At the time of polymerisation conversion becomes 96%, cooled down and terminate reaction, obtained non-aqueous It is secondary cell adhesive composition (aqueous solution of water-soluble polymer).It is water-soluble using the adhesive composition, measure Swellbility and glass transition temperature of the polymer in non-aqueous electrolyte.Show the result in table 1.
<The preparation of the aqueous dispersions of particle shaped polymer>
In the reactor with mixer, be supplied respectively to 70 parts ion exchange water, 0.15 part as emulsifying agent (manufacture of Kao Chemicals companies, " Emal 2F " and 0.5 part of ammonium persulfate, uses nitrogen to ProductName to lauryl sodium sulfate Gas phase portion is replaced, is heated to 60 DEG C.
On the other hand, in other container, using 50 parts of ion exchange water, 0.5 part of the dodecane as dispersant Base benzene sulfonic acid sodium salt and 94 parts of butyl acrylate, 2 parts of acrylonitrile, 2 parts of methacrylic acid, 1 part of N- methylol propylene Acid amides and the mixing of 1 part of acrylamide, obtain monomer mixture.By the monomer mixture after 4 it is small when be added continuously to State in reactor and polymerize.In adding procedure, reacted with 60 DEG C.After terminating addition, further 3 are stirred at 70 DEG C Hour and reaction was completed, prepare comprising as particle shaped polymer acrylic acid series polymeric compounds aqueous dispersions.In addition, with it is water-soluble Property polymer the glass transition temperature glass transition temperature of acrylic acid series polymeric compounds that similarly carries out and measure be -40 ℃。
<The preparation of non-aqueous secondary battery functional layer composition>
Relative to 100 parts as non-conductive particles alumina filler (manufacture of Japanese light metal company, " LS256 ") mixing with solid constituent a great deal of is calculated as 5 parts of above-mentioned water-soluble polymer, is calculated as 2 parts with solid constituent a great deal of Above-mentioned particle shaped polymer, 0.2 part of polyethylene glycol type surfactant (Sannopco companies manufacture, " Sannopco (note Volume trade mark) SN Wet 366 "), prepare functional layer composition.In addition, by the mixing, generation comprising water-soluble polymer and The adhesive composition of particle shaped polymer, in other words, in obtained functional layer composition, containing including water-soluble polymeric The adhesive composition of thing and particle shaped polymer.
<Functional layer and with functional layer distance piece making>
Prepare organic spacer part base material (manufacture of Celgard companies, 16 μ of thickness formed by the porous substrate of polyethylene M) it is used as distance piece base material.Above-mentioned functional layer composition is applied on the distance piece base material, it is dried 10 points at 60 DEG C Clock.Thus, the distance piece of the functional layer with 2 μm of thickness on distance piece base material is obtained.Using the distance piece, to functional layer Cementability, transition metal before electrolyte dipping and after dipping catch energy and the thermal shrinkage of distance piece is evaluated.Will The results are shown in table 1.
<The preparation of anode>
In the 5MPa pressure vessels with mixer, add 33 parts 1,3-butadiene, 3.5 parts of itaconic acid, 63.5 Styrene, 0.4 part of the neopelex, 150 parts of ion exchange water and 0.5 part of conduct as emulsifying agent of part The potassium peroxydisulfate of polymerization initiator, after being sufficiently stirred, is heated to 50 DEG C, triggers polymerization.When polymerisation conversion becomes 96% Carve, cooled down and terminate reaction, obtain the mixture of the particle shape binding material (SBR) comprising anode material layer. Above-mentioned comprising in the mixture of particle shape binding material, after pH is adjusted to 8 by 5% sodium hydrate aqueous solution of addition, pass through Heating vacuum distillation, carries out the removing of unreacted monomer.It is then cooled to less than 30 DEG C, obtain including desired particle shape The aqueous dispersions of binding material.
Then, using 100 parts of Delanium (the volume average particle size D50 as negative electrode active material：15.6 μm), with solid Body component a great deal of is calculated as 1 part of the sanlose (Nippon Paper company system " MAC350HC ") as tackifier 2% aqueous solution and ion exchange water mixing, after solid component concentration is adjusted to 68%, mix 60 minutes at 25 DEG C.Then, use After solid component concentration is adjusted to 62% by ion exchange water, further mixed 15 minutes at 25 DEG C.Then, in obtained mixing In liquid, add and 1.5 parts of the above-mentioned aqueous dispersions and ion that include particle shape binding material are calculated as with solid constituent a great deal of Exchanged water, is adjusted, further mixing 10 minutes in a manner of final solid component concentration becomes 52%.Under reduced pressure to it Deaeration processing is carried out, obtains the negative electrode slurry composition of good fluidity.
Then, with unfilled corner wheel coating machine by it is above-mentioned carry out like that obtained from negative electrode slurry composition with dried Thickness is coated on the copper foil as 20 μm of the thickness of collector as 150 μm or so of mode, it is dried, is born Pole raw material.The drying is carried out by the way that copper foil to be transported in 60 DEG C of baking oven to 2 minutes with the speed of 0.5m/ minutes.Then, lead to Cross roller press to roll anode raw material, the thickness for obtaining anode material layer is 80 μm of anode.
<The preparation of cathode>
By 100 parts of LiCoO as a positive electrode active material2(volume average particle size D50：12 μm), 2 parts of conduct it is conductive The acetylene black (Denki Kagaku Kogyo kabushiki's system " HS-100 ") of material, be calculated as using solid constituent a great deal of 2 parts and answered as cathode The Kynoar (manufacture of Kur eha companies, #7208) of the binding material of condensation material layer and 1-methyl-2-pyrrolidinone mixing, All solids constituent concentration is set to 70%.They are mixed by planetary stirring machine, prepares cathode paste compound.
With unfilled corner wheel coating machine by it is above-mentioned carry out like that obtained from cathode paste compound with dried thickness As 150 μm or so of modes coated on the aluminium foil as 20 μm of the thickness of collector, it is dried, obtains cathode original Material.The drying by the way that aluminium foil is transported 2 minutes in 60 DEG C of baking oven with the speed of 0.5m/ minutes, and then at 120 DEG C of heating 2 minutes are managed to carry out.Then, cathode raw material is rolled by roller press, the thickness for obtaining anode composite material layer is 80 μm of cathode.
<The manufacture of lithium rechargeable battery>
The pressed cathode obtained in will be above-mentioned is cut out as 49cm × 5cm, using the surface of anode composite material layer side as The mode of upside is placed.Then, configure to cut out as follows on it (has for the distance piece of 120cm × 5.5cm in single side The distance piece of functional layer), i.e. the surface of the anode composite material layer side of cathode and the functional layer of distance piece are opposite and cathode is located at On the left of the long dimensional directions of distance piece.And then will be above-mentioned in obtained pressed anode cut out as 50cm × 5.2cm, by it Configure as follows on distance piece, i.e. the surface of anode material layer side and the organic spacer part base material phase of distance piece To and anode be located on the right side of the long dimensional directions of distance piece.By up- coiler by it with the pars intermedia of the long dimensional directions of distance piece Centered on wind, obtain coiling body.Under conditions of 60 DEG C, 0.5MPa, which is suppressed, bluff body is made, so Afterwards, the aluminium packaging material outer packing parcel of the outer packing of battery is used as, by electrolyte (solvent：EC/DEC/VC (volume ratio)= 68.5/30/1.5, electrolyte：The LiPF of concentration 1M6) injected in a manner of not residual air.And then for sealed aluminum packing timber The opening of material outer packing, carries out 150 DEG C of heat-sealing and sealed aluminum packaging material outer packing, manufacture discharge capacity are 1000mAh's Winding type lithium ion secondary cell is as non-aqueous secondary battery.
Then, circulation is evaluated to obtained secondary cell.Show the result in table 1.
(embodiment 2~7)
When preparing non-aqueous secondary battery adhesive composition, by the species of the monomer used and the ratio such as institute of table 1 Show change, in addition, carry out similarly to Example 1, manufacture adhesive composition, functional layer composition, functional layer, tool Distance piece, anode, cathode and the lithium rechargeable battery of active ergosphere.Then, various evaluations are carried out similarly to Example 1. Show the result in table 1.In addition, in example 4, use sodium styrene sulfonate to be used as and contained sulfonic monomer.
(comparative example 1~4)
When preparing non-aqueous secondary battery adhesive composition, by the species of the monomer used and the ratio such as institute of table 1 Show change, in addition, carry out similarly to Example 1, manufacture adhesive composition, functional layer composition, functional layer, tool Distance piece, anode, cathode and the lithium rechargeable battery of active ergosphere.Then, various evaluations are carried out similarly to Example 1. Show the result in table 1.In addition, in comparative example 3 and 4, in the preparation of non-aqueous secondary battery adhesive composition, no It is to have obtained water-soluble polymer but obtained water-insoluble polymer.In addition, in comparative example 4, used acrylic acid- 2- ethylhexyls are used as (methyl) acrylate monomer.
In addition, in table 1 as shown below,
" LiSS " represents styrene sulfonic acid lithium,
" NaSS " represents sodium styrene sulfonate,
" AN " represents acrylonitrile,
" BA " represents butyl acrylate,
" 2-EHA " represents acrylic acid-2-ethyl caproite,
" MAA " represents methacrylic acid,
" ACL " represents acrylic acid series polymeric compounds.
[table 1]
According to the embodiment 1~7 of above-mentioned table 1 and comparative example 1~4, if using following water-soluble polymer As binding material, then can form transition metal and catch can be excellent and can make secondary cell play excellent cycle characteristics Functional layer, what above-mentioned water-soluble polymer included more than 10 mass % and below 50 mass % contains sulfonic monomeric unit, And (methyl) acrylonitrile monomer unit comprising more than 20 mass %.In addition we know, obtained using the water-soluble polymer Functional layer front and rear excellent in adhesion of electrolyte dipping, the thermal shrinkage of the distance piece with the functional layer is excellent in addition It is different.
Moreover, according to the embodiment 1~7 of above-mentioned table 1, by preparing non-aqueous secondary battery binding agent group Change species, the ratio of the monomer used during compound (aqueous solution of water-soluble polymer), so as to make the transition of functional layer golden The cycle characteristics for belonging to the front and rear cementability of seizure energy, electrolyte dipping, the thermal shrinkage of distance piece and secondary cell is further Improve.
Industrial applicability
In accordance with the invention it is possible to provide the functional layer and electrode composite material that can be formed and energy is caught with high transition metal The non-aqueous secondary battery adhesive composition of layer.
In addition, in accordance with the invention it is possible to provide the non-water system that can form the functional layer that energy is caught with high transition metal Secondary cell functional layer composition.
Moreover, used in accordance with the invention it is possible to provide the non-aqueous secondary battery with high transition metal seizure energy Layer and with the non-aqueous secondary battery functional layer and the excellent non-aqueous secondary battery of the battery behavior such as cycle characteristics.

Claims (7)

  1. A kind of 1. non-aqueous secondary battery adhesive composition, it is characterised in that containing water-soluble polymer and water,
    The water-soluble polymer includes the sulfonic monomeric unit that contains of more than 10 mass % and below 50 mass %, and (methyl) acrylonitrile monomer unit comprising more than 20 mass %.
  2. 2. non-aqueous secondary battery adhesive composition according to claim 1, wherein, the water-soluble polymer exists Swellbility in non-aqueous electrolyte is more than 2 times and less than 5 times.
  3. 3. non-aqueous secondary battery adhesive composition according to claim 1 or 2, wherein, further contain particle Shaped polymer.
  4. 4. a kind of non-aqueous secondary battery functional layer composition, contains non-water system two according to any one of claims 1 to 3 Primary cell adhesive composition and non-conductive particles.
  5. 5. non-aqueous secondary battery functional layer composition according to claim 4, wherein, relative to 100 mass parts The non-conductive particles, containing more than 1 mass parts and 10 water-soluble polymers below mass part.
  6. 6. a kind of non-aqueous secondary battery functional layer, it is the non-aqueous secondary battery functional layer described in usage right requirement 5 Formed with composition.
  7. 7. a kind of non-aqueous secondary battery, has the non-aqueous secondary battery functional layer described in claim 6.
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